Polyetherimide with reactive branching

Abstract

A first repeat unit derived from the polymerization of an aromatic dianhydride and a first diamine, the first diamine comprising a carboxyl-substituted C 6-24 a first repeat unit comprising an aromatic hydrocarbon group and, optionally, a second repeat unit derived from the polymerization of an aromatic dianhydride and a second diamine, the second diamine being C 1-30 and a second repeat unit comprising a divalent hydrocarbon group (optionally containing 1 to 4 heteroatoms), wherein the self-branched polyetherimide is endcapped with phthalic anhydride.

Description

[Technical field]

[0001] The present invention relates to polyetherimides having reactive branching.

[0002] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority and benefit of European Patent Application No. 21213483.7, filed in the European Patent Office on December 9, 2021, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] Polyimides (PIs) are typically classified as high-performance polymers, possessing high-temperature stability (>450 °C), thermomechanical properties, mechanical performance, and high aromatic composition. Although PIs have many of the properties required for applications in automotive, aerospace, electronics, and consumer applications, the rigid aromatic backbone presents processing challenges such as insolubility or limited melt flow at typical processing temperatures and shear rates. Thus, these polymers must be produced using high energy consumption or require modification of the backbone composition to improve processability. Recently, advances in additive manufacturing (also known as three-dimensional (3D) printing) development provide new avenues for the production of previously difficult-to-process PIs.

[0004] The processability of PI can be improved by incorporating flexible linkages, such as ether and / or isopropylidene / hexafluoro-isopropylidene, in the backbone. Commonly known as polyetherimides (PEIs), these high-performance thermoplastics offer ease of injection molding and other processing while maintaining desirable thermal and mechanical properties. Other methods can be used to improve the processability of PEI. Incorporation of thioether linkages increases backbone flexibility but can often reduce thermal stability. Long chain branching (LCB) can improve shear thinning behavior at processing shear rates, but careful consideration is required to avoid crosslinking during the synthesis of PEI. Reducing chain packing and alignment by modification of backbone regiochemistry, pendant groups, or bulky halogenated monomers can sometimes improve processability, but it can also increase cost and reduce mechanical properties. Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, there is a continuing need for polyetherimides that have improved processability, high temperature stability, and excellent mechanical properties. [Means for solving the problem]

[0006] Provided is a self-branching polyetherimide, the self-branching polyetherimide comprising a first repeat unit derived from the polymerization of an aromatic dianhydride and a first diamine, the first diamine being a carboxyl-substituted C 6-24 and optionally a second repeat unit derived from the polymerization of an aromatic dianhydride and a second diamine, the second diamine being selected from the group consisting of C 1-30 The self-branched polyetherimide, which contains a divalent hydrocarbon group (optionally containing 1 to 4 heteroatoms), is end-capped with phthalic anhydride.

[0007] Also provided is a branched polyetherimide derived from the thermal decarboxylation and crosslinking of the self-branched polyetherimide, which may also be referred to herein as a self-branched polyetherimide.

[0008] Another embodiment is a dianhydride of formula (5): [ka] (5) or its chemical equivalent, with a first diamine, optionally a second diamine, and phthalic anhydride, wherein the first diamine is represented by formula (6): [ka] (6) In the formula, each L 1 are independently a single bond or a divalent linking group, and each R 3 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted C 1-30 heteroaryl, preferably hydrogen, and n is an integer from 1 to 3, or from 1 to 2; preferably the divalent linking group is a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 1-30 Heteroarylene, -O-, -C(O)-, -C(O)-O-, -N(R 2b )-, -S-, or -S(O) 2 -, wherein R 2b is hydrogen, linear or branched C 1-20 Alkyl, monocyclic or polycyclic C3-20 Cycloalkyl, or monocyclic or polycyclic C 1-20 It is a heterocycloalkyl.

[0009] Yet another embodiment provides a method for producing a self-branched polyetherimide comprising the step of heating a self-branched polyamic acid to form a self-branched polyetherimide.

[0010] Yet another aspect provides an article comprising a branched polyetherimide derived from a self-branched polyetherimide, a branched polyetherimide, or a branched polyetherimide derived from a self-branched polyamic acid. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Polymers with latent reactive pendant groups or reactive end cappers (terminal groups) can react during or after processing to form products with the desired properties of more difficult to process compositions. Reactive extrusion and post-processing utilize reactive functional groups that are typically activated at high temperatures to increase molecular weight or promote crosslinking during or after processing. This helps facilitate processing while maintaining the final desired properties after completion. Common functional groups include various phenylethynyl structures as chain end-cappers due to their high temperature stability and tunability.

[0012] Long chain branching (LCB) affects polymer melt strength and shear thinning behavior, both of which contribute to polymer processability. Lower branching density reduces coil size, promoting lower viscosity and faster shear thinning at similar molecular weight and processing temperature. Thus, PEI incorporating LCB provides an avenue to tailor rheological performance while increasing melt flow properties. The inventors have discovered that melt processing induced branching using lower molecular weight functionalized PEI can provide higher molecular weight branched PEI with zero shear viscosity during or after processing. PEIs typically have desirable flame retardancy due to their highly aromatic composition, and this flame retardancy rating increases based on higher molecular weight, thus the inventors have discovered a way to improve both flame retardancy and processability.

[0013] One embodiment provides a self-branched polyetherimide. The self-branched polyetherimide is a melt-processable polymer incorporating reactive pendant carboxylic acid functional groups. The reactive pendant carboxylic acid group(s) provide branching points for branching the self-branched polyetherimide in the molten state. The resulting melt-processed product of the self-branched polyetherimide is a branched polyetherimide (or self-branched polyetherimide). In other words, the self-branched polyetherimide is a linear polymer until the melt-processing step, during which thermal decarboxylation and crosslinking results in the self-branched polyetherimide. Without wishing to be bound by theory, the pendant carboxylic acid group(s) may undergo decarboxylation, inducing crosslinking of the self-branched polyetherimide to form a branched polyetherimide. Thus, the self-branched polyetherimide provides a reaction pathway to produce branched polyetherimides with long chain branching. The resulting branched polyetherimide provides a film that achieves improved flame retardancy, for example, with no dripping and short after-flame time.

[0014] As used herein, the term "self-branched polyetherimides" refers to polyetherimides that contain reactive carboxylic acid functional groups or derivatives thereof that are capable of self-branching. At elevated temperatures, these functional groups decarboxylate and form biphenyl units or other crosslinks by radical coupling. As used herein, the term "crosslinking" refers to the thermal reaction of the self-branching moieties (i.e., carboxylic acid groups or derivatives thereof). Self-branched polyetherimides, as described above, are linear when produced and undergo crosslinking at the reactive carboxylic acid sites to form branched polyetherimide products. Unlike other long-chain branched polyimides and polyetherimides that can be synthesized directly using trivalent or higher valent polyamine branching groups, the self-branched polyetherimides of the present disclosure do not use polyamines as long-chain branching points.

[0015] The self-branched polyetherimide comprises a first repeat unit derived from the polymerization of an aromatic dianhydride and a first diamine, the first diamine comprising a carboxyl-substituted C 6-24 The self-branched polyetherimide containing aromatic hydrocarbon groups is end-capped with phthalic anhydride.

[0016] The first repeat unit of the self-branched polyetherimide, which for convenience will be referred to as a polyetherimide unless otherwise indicated by the context of subsequent use, can be represented by formula (1): [ka] (1) wherein the Z group in -OZO- is a divalent organic group, optionally containing an aromatic C substituted with 1 to 6 heteroatoms, 1 to 8 halogen atoms, or a combination thereof. 6-24 It can be a monocyclic or polycyclic moiety, provided that the valence of Z is not exceeded. The divalent bonds of the -OZO- group are in the 3,3', 3,4', 4,3', or 4,4' positions. Exemplary Z groups include groups derived from dihydroxy compounds of formula (4): [ka] (4) In the formula, R a and R b may be the same or different and are halogen atoms or monovalent C 1-6 For example, p' and q' are each independently an integer from 0 to 4, c is from 0 to 4, and X a may be a bridging group linking the hydroxy-substituted aromatic groups, and each C 6 The bridging group and hydroxy substituent of the arylene group are 6 The bridging group X may be arranged ortho, meta, or para (preferably para) to each other on the arylene group. a is a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)-, or C 1-18 It may be an organic bridging group. 1-18 The organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further contain halogens and / or heteroatoms such as oxygen, nitrogen, sulfur, silicon, or phosphorus. 1-18 The organic group has a C bonded to it. 6 Each arylene group is 1-18 They can be arranged to be linked to a common alkylidene carbon or to different carbons of the organic bridging group. An illustrative example of a Z group is a divalent group of formula (4a): [ka] (4a) In the formula, J is -O-, -S-, -C(O)-, -SO 2 -, -SO-, or -C y H 2y -, where y is an integer from 1 to 5, or a halogenated derivative thereof, including a perfluoroalkylene group. In certain embodiments, Z is derived from bisphenol A, such that J in formula (3a) is 2,2-isopropylidene.

[0017] In formula (1), each R 1 are independently a group of formula (3) [ka] (3) In the formula, each L 1 is independently a single bond or a divalent linking group, and n is an integer from 1 to 3, or from 1 to 2. 1 is a single bond or a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 1-30 Heteroarylene, -O-, -C(O)-, -C(O)-O-, -N(R 2b )-, -S-, or -S(O) 2 -, where R 2b is hydrogen, linear or branched C 1-20 Alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 1-20 Heterocycloalkyl. Each R 3 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted C 1-30 Heteroaryl, preferably hydrogen. For example, each R 1 may independently be a group of formula (3a): [ka] (3a) In the formula, each R 3 is as defined for formula (3), and n1 is an integer from 1 to 3, or from 1 to 2. In some embodiments, each R 1 may independently be a group of formula (3b): [ka] (3b) In the formula, R 3 is as defined for formula (3). Even more preferably, each R 1 are independently a group of formula (3c) [ka] (3c)

[0018] The self-branched polyetherimide optionally further comprises a second repeat unit derived from the polymerization of an aromatic dianhydride and a second diamine, the second diamine being C 1-30 For example, the second repeat unit may be represented by formula (2): [ka] (2) wherein each Z can be a group described above for formula (1). In some embodiments, the Z group is the same in both the first repeat unit and the second repeat unit.

[0019] In formula (2), each R 2 is independently C 1-30 A divalent hydrocarbon group (optionally containing 1 to 4 heteroatoms). For example, each R 2 are the same or different C 6-24 Aromatic hydrocarbon radicals or their halogenated derivatives, linear or branched C 2-20 Alkylene group or its halogenated derivative, C 3-8 A cycloalkylene group or a halogenated derivative thereof, in particular a divalent group of one of the following formulae: [ka] In the formula, Q 1 -O-, -S-, -C(O)-, -SO 2 -, -SO-, -P(R k )(=O)-(wherein, R k is C 1-8Alkyl or C 6-12 aryl), -C y H 2y -(wherein y is an integer from 1 to 5) or a halogenated derivative thereof (including a perfluoroalkylene group), or -(C 6 H 10 ) z - (wherein z is an integer from 1 to 4). In certain embodiments, each R 2 is independently meta-phenylene, para-phenylene, bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone, or bis(3,3'-phenylene)sulfone.

[0020] When the self-branched PEI is a copolymer comprising a first repeat unit of formula (1) and a second repeat unit of formula (2), the first repeat unit can be present in an amount of 0.01 to 100 mole percent (mol%), or 1 mol% to 75 mol%, or 10 mol% to 50 mol%, based on 100 mol% total repeat units in the PEI. For example, the self-branched PEI can comprise 0.01 mol% to 100 mol%, or 1 mol% to 75 mol%, or 10 mol% to 50 mol% of the first repeat unit, and 0 mol% to 99.99 mol%, or 25 mol% to 99 mol%, or 50 mol% to 90 mol% of the second repeat unit.

[0021] Self-branched PEI is a copolymer, e.g., at least 50 mol % of the repeat units in the PEI have the formula (1) and the remaining 50 mol % of the repeat units in the PEI have the formula (2), Q 1 -SO 2 Alternatively, the self-branched polyetherimide can be a copolymer containing additional structural imide units, for example imide units where V has the formula: [ka] In the formula, W is a single bond, -O-, -S-, -C(O)-, -SO2 -, -SO-, -P(R j )(=O)-(wherein, R j is C 1-8 Alkyl or C 6-12 aryl), or -C y H 2y -, where y is an integer from 1 to 5, or halogenated derivatives thereof, including perfluoroalkylene groups. These additional structural imide units can account for less than 20 mol%, or from 0 mol% to 10 mol%, or from 0 mol% to 5 mol%, or from 0 mol% to 2 mol% of the total number of repeat units in the polyimide, based on a total of 100 mol%. In some embodiments, there are no additional imide units other than polyetherimide units.

[0022] Polyetherimides can be prepared by methods known in the art, including polycondensation or ether-forming polymerization.

[0023] In one or more embodiments, the polyimides can be prepared by polycondensation, which involves the reaction of a dianhydride of formula (5): [ka] (5) or its chemical equivalent, a first diamine of formula (6) [ka] (6) and, optionally, a diamine of formula (7) H 2 NR 2 -NH 2 (7) by, imidization in a solvent under conditions effective to provide a self-branched polyetherimide, wherein n is an integer from 1 to 3, or from 1 to 2, or 1; Z, L 1 , R 2 , and R 3 is as described herein.

[0024] For example, the first diamine can be represented by formula (6a): [ka] (6a) where n1 is an integer from 1 to 3, or from 1 to 2, or 1; R 3 is as defined herein. In some embodiments, the first diamine is represented by formula (6b): [ka] (6b) In the formula, R 3 is as defined herein, preferably hydrogen.

[0025] Exemplary dianhydrides of formula (5) include 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride, and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, or combinations thereof.

[0026] Specific examples of the diamine of formula (7) include the following: hexamethylenediamine, polymethylated 1,6-n-hexanediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 5-methylnonamethylenediamine, 6-methylnonamethylenediamine, 7-methylnonamethylenediamine, 8-methylnonamethylenediamine, 9-methylnonamethylenediamine, 10-methylnonamethylenediamine, 11-methylnonamethylenediamine, 12-methylnonamethylenediamine, 13-methylnonamethylenediamine, 14-methylnonamethylenediamine, 15-methylnonamethylenediamine, 16-methylnonamethylenediamine, 17-methylnonamethylenediamine, 18-methylnonamethylenediamine, 19-methylnonamethylenediamine, 20-methylnonamethylenediamine, 21-methylnonamethylenediamine, 22-methylnonamethylenediamine, 23-methylnonamethylenediamine, 24-methylnonamethylenediamine, 25-methylnonamethylenediamine, 26-methylnonamethylenediamine, 27-methylnonamethylenediamine, 28-methylnonamethylenediamine, 29-methylnonamethylenediamine, 30-methylnonamethylenediamine, 31-methylnonamethylenediamine, 32-methylnonamethylenediamine, 33-methylnonamethylenediamine, 34-methylnonamethylenediamine, 35-methylnonamethylenediamine, 36-methylnonamethylenediamine, 37-methylnonamethylenedi Hexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl)methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene benzene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl)methane, bis(2-chloro-4-amino-3,5-diethylphenyl)methane, bis(4-aminophenyl)propane, 2,4-bis(p 4'-amino-t-butyl)toluene, bis(p-amino-t-butylphenyl)ether, bis(p-methyl-o-aminophenyl)benzene, bis(p-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, bis(4-aminophenyl)sulfide, bis-(4-aminophenyl)sulfone (also known as 4,4'-diaminodiphenylsulfone (DDS)), bis(4-aminophenyl)ether, or combinations thereof. Any positional isomer of said compounds can be used. For example, the diamine of formula (7) can be m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, or combinations thereof.

[0027] A catalyst can be present during the imidization. Exemplary catalysts include: sodium arylphosphinate, guanidinium salts, pyridinium salts, imidazolium salts, tetra(C 7-24 arylalkylene) ammonium salts, dialkylheterocycloaliphatic ammonium salts, bis-alkyl quaternary ammonium salts, (C 7-24 Aryl alkylene) (C 1-16 alkyl)phosphonium salts, (C 6-24 Aryl)(C 1-16 alkyl)phosphonium salts, phosphazenium salts, and combinations thereof. The anion can be, for example, chloride, bromide, iodide, sulfate, phosphate, acetate, maculate, tosylate, and the like, or combinations thereof. The amount of catalyst can be, for example, 0.01 to 5 mol%, or 0.05 to 2 mol%, or 0.2 to 1 mol%, based on the moles of diamine (6) or (7).

[0028] Polyetherimides can be prepared by polymerization in a solvent, for example, a relatively non-polar solvent having a boiling point above 100° C., or above 150° C., such as o-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, dimethylacetamide, diphenyl sulfone, anisole, veratrole, diphenyl ether, N-methylpyrrolidone, phenetole, and the like, or combinations thereof. The polymerization can be carried out at a temperature of at least 110° C., or from 150 to 275° C., or from 175 to 225° C., for solution polymerization. Atmospheric or superatmospheric pressures, for example up to 500 kilopascals (kPa), can be used to minimize solvent loss. Reaction times vary depending on the reactants and conditions and can be from 0.5 hours (h) to 3 days, or from 0.5 to 72 hours, or from 1 to 30 hours, or from 1 to 20 hours, or up to 20 hours, or up to 10 hours, or up to 3 hours.

[0029] Phthalic anhydride (PA) endcapping agent can be added to the polymerization in the range of greater than 0 mol% to 20 mol%, or 1 mol% to 10 mol%, based on the amount of diamine (6) and optional diamine (7). The endcapping agent can be added at any time. For example, the endcapping agent can be mixed with or dissolved in reactants having similar functionality, e.g., an anhydride-containing endcapping agent is combined with dianhydride (5). To achieve maximum molecular weight, the amount of amine functionality [2 x moles of diamine] = moles of anhydride functionality ([2 x moles of dianhydride + moles of anhydride in the endcapping agent]).

[0030] The molar ratio of dianhydride (5) to the combination of diamine (6) and, optionally, diamine (7) can be from 0.9:1 to 1.1:1, or even 1:1.

[0031] Polyetherimides can be synthesized by ether-forming polymerization, which proceeds via imidization, i.e., reaction of diamines of formula (6) and, optionally, (7), with anhydrides of formula (10). [ka] (10) wherein X is a nitro group or a halogen, providing an intermediate bis(phthalimide) of formula (11): [ka] In the formula, R is R in formula (1). 1 and optionally R in formula (2) 2 and X is as described in formula (10). An optional catalyst or an optional monofunctional chain terminator as described above can be present during the imidization.

[0032] The bis(phthalimide) (11) is then reacted with an alkali metal salt of a dihydroxyaromatic compound of formula (12): AMO-Z-OAM (12) where AM is an alkali metal and Z is as defined herein, an anhydride-capped oligomer is provided, and the anhydride-capped oligomer is optionally reacted with an amino compound (8) under conditions effective to provide a polyetherimide. Polymerization conditions effective to provide a polyetherimide are generally known and can be carried out in the solvents described above. The polymerization can also be carried out in the melt, for example at 250° C. to 350° C., in which case a solvent is generally not present.

[0033] Also provided is a polyamic acid solution comprising 1 to 99 weight percent (wt%), or 10 wt% to 90 wt%, or 0.1 wt% to 20 wt%, or 0.5 wt% to 10 wt%, or 1 wt% to 5 wt% of a self-branched polyamic acid derived from the condensation reaction of a dianhydride of formula (5), a diamine of formula (6), optionally a diamine of formula (7), and phthalic anhydride, and a solvent. The polyamic acid solution can be prepared by combining the dianhydride (5), the diamine components of formula (6) and optionally (7), phthalic anhydride, and a solvent with stirring until a viscous solution is formed. For example, a method of making a polyamic acid solution can include combining the components and heating with stirring or agitation at a temperature and for a period of time effective to dissolve the components in the solvent or at a temperature below the boiling point of the solvent. The temperature is not particularly limited and can be selected to avoid instability of the polyamic acid. Preferably the temperature is below 50°C, or below 30°C, or below 25°C.

[0034] For example, a self-branched polyamic acid film can be prepared by casting a polyamic acid solution onto a substrate and removing the solvent from the cast layer. The solvent can be removed by a number of means, including heating the cast layer or heating the cast layer under heat and pressure. The self-branched polyamic acid film can then be imidized using a heat treatment to form a self-branched PEI, which can then undergo curing to form the branched PEI described herein. For example, a solution cast sample of the self-branched polyamic acid can form a self-branched polyetherimide at a temperature of 250°C to 300°C, or 260°C to 300°C, or 265°C to 300°C, as determined by thermogravimetric analysis (TGA).

[0035] The self-branched polyetherimide may have one or more of the following characteristics: The self-branched polyetherimide has a glass transition temperature (T) of greater than 200° C., or from 200° C. to 400° C., or from 220° C. to 400° C., or from 220° C. to 360° C., as determined by differential scanning calorimetry (DSC). g ), and a thermal decomposition temperature (T) of greater than 450°C, or between 450°C and 550°C, or between 500°C and 550°C, as determined by thermogravimetric analysis (TGA) at 5% weight loss. d ).

[0036] The branched polyetherimide may have one or more of the following properties: The branched polyetherimide may have a glass transition temperature greater than 160° C., or from 160° C. to 300° C., or from 180° C. to 250° C., or from 200° C. to 250° C., as determined by DSC, and a flame retardant rating of V0 at a thickness of 0.8 mm, or a flame retardant rating of V0 at a thickness of 0.6 mm, or a flame retardant rating of V0 at a thickness of 0.4 mm, as measured according to ASTM D3801.

[0037] In another embodiment, a polymer composition is provided. The composition can include a self-branched or branched polyetherimide and a second polymer. Such a polymer composition can include 1 wt% to 99 wt% of the self-branched or branched polyetherimide and 1 wt% to 99 wt% of the second polymer, or 10 wt% to 90% of the self-branched or branched polyetherimide and 10 wt% to 90 wt% of the second polyimide, based on the total weight of the composition excluding the solvent.

[0038] Illustrative examples of the second polymer include, but are not limited to, polyacetal, poly(C 1-6 alkyl) acrylate, polyacrylamide, polyacrylonitrile, polyamide, polyamideimide, polyanhydride, polyarylene ether, polyarylene ether ketone, polyarylene ketone, polyarylene sulfide, polyarylene sulfone, polybenzothiazole, polybenzoxazole, polybenzimidazole, polycarbonate, polyester, poly(C 1-6 alkyl) methacrylates, polymethacrylamides, cyclic olefin polymers, polyolefins, polyoxadiazoles, polyoxymethylenes, polyphthalides, polyimides, polysilazanes, polysiloxanes, polystyrenes, polysulfides, polysulfonamides, polysulfonates, polythioesters, polytriazines, polyureas, polyurethanes, vinyl polymers, and the like, or combinations thereof.

[0039] The polymeric compositions can contain a variety of additives that are typically incorporated into these types of compositions, provided that any additive is selected so as not to significantly adversely affect the desired properties of the composition. Exemplary additives include: antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) absorbing additives, quenchers, plasticizers, lubricants, mold release agents, antistatic agents, visual effect additives such as dyes, pigments, and lighting effect additives, flame retardants, anti-drip agents, and radiation stabilizers. Particulate and reinforcing fillers may also be present, including mineral fillers, flake fillers, carbon nanotubes, exfoliated nanoclays, carbon nanowires, carbon nanospheres, carbon metal nanospheres, carbon nanorods, carbon metal nanorods, nanoparticles, insoluble polymers, glass fibers, carbon fibers, glass-carbon fibers, talc, e.g., fibrous, modular, acicular, and lamellar talc, graphite, fibrillated fluoropolymers, polymer fibers and filaments, woven fibers, metal particles, inorganic fibers, single crystal fibers or "whiskers", and the like. Combinations of additives may be used. The additives may be present individually in amounts of 0.005 wt% to 10 wt%, or in combination in amounts of 0.005 wt% to 20 wt%, or 0.01 wt% to 10 wt%, based on the total weight of the composition.

[0040] Also provided herein are articles comprising branched polyetherimides obtained from self-branched polyetherimides, branched polyetherimides, branched polyetherimides obtained from self-branched polyamic acids, polymer compositions described herein, or combinations thereof. A wide variety of articles can be produced, such as articles useful in automotive, telecommunications, aerospace, electrical / electronics, battery manufacturing, wire coating, transportation, food industry, and health care applications. Such articles can include films, membranes, fibers, foams, sheets, conductive parts, coatings, preforms, composites, varnishes, lenses, and the like. For example, the article can be an open or closed cell foam, nanofoam, battery separator, ion exchange membrane, tubing, capillary, antistatic coating, self-cleaning surface, antifouling surface, or scratch-resistant part. Another specific example is a separator for a secondary battery, such as a lithium ion battery. The article can be extruded or molded, such as injection molding, melt extrusion, thermoforming, or rotomolding. The article can be produced by additive manufacturing methods, such as 3D printing. Components for electronic devices and components for sterilizable medical articles are particularly useful. Thin-walled components made by injection molding, for example walls having a thickness of 0.1 mm to 10 mm, or 0.2 mm to 5 mm, or 0.5 mm to 2 mm, are useful.

[0041] The self-branched or branched polyetherimides and polyamic acids are further illustrated by the following non-limiting examples. EXAMPLES

[0042] Table 1 lists the ingredients used in the examples.

[0043] [Table 1]

[0044] Physical testing of the compositions was performed according to the following test methods and procedures. Unless otherwise stated, all test standards specified herein are current as of 2016.

[0045] Proton nuclear magnetic resonance ( 1 H NMR spectroscopy was performed at 23 °C on a Varian Unity 400 at 400 MHz using deuterated chloroform (CDCl 3 ) or deuterated dimethyl sulfoxide (DMSO-d 6 ) for use in the experiment.

[0046] Advanced Permeation Chromatography (APC) was performed using a Waters ACQUITY equipped with 450 Å × 150 mm, 200 Å × 150 mm, and 125 Å × 150 mm XT columns and a Waters ACQUITY RI detector at a flow rate of 1.0 mL / min at 40 °C with CHCl 3 Prior to APC analysis, dynamic light scattering (DLS) was used at 40° C. to obtain molecular weights relative to polystyrene standards. 3 It was demonstrated that all polymer solutions in the study did not exhibit aggregation.

[0047] Glass transition temperature (T g ) was determined using differential scanning calorimetry (DSC) under nitrogen according to ASTM D3418. The test was carried out using a DSC Q2000 DSC instrument by heating from -10°C to 300°C at a rate of 10°C / min, and T g The value was determined by the inflection point from the second thermal cycle.

[0048] Dynamic mechanical analysis (DMA) revealed the elastic modulus versus temperature behavior using a TA Instruments Q800 dynamic mechanical analyzer in oscillatory tension mode with a frequency of 1 Hz, an oscillation amplitude of 15 μm, and a static force of 0.01 N, using a 3° C. / min heating ramp. Stepwise isothermal analysis was performed by DMA to determine the imidization temperature (T im ) was searched for. g was also determined by DMA, where specified.

[0049] Thermogravimetric analysis (TGA) was used to determine the thermal decomposition temperature on a Discovery TGA Q500. Samples were heated from 25°C to 600°C at a heating rate of 10°C / min in a stream of nitrogen (25mL / min). Stepwise isothermal analysis was performed at 10°C min -1 Heating rate and weight percent change are >0.1%min -1 In this case, an isothermal process is used and the weight percent change is <0.01%min. -1 Heating was resumed as soon as this occurred. A TGA coupled to a Thermo-Fisher Nicolet iS-10 Fourier transform infrared spectrometer (TGA-FTIR) analyzed the evolved gases of a 20 mg sample heated at 20 °C / min. Isothermal steps were used for 30 min between solvent evaporation / imidization and decarboxylation, and between decarboxylation and backbone decomposition, to separate the FTIR analysis of the various off-gas components.

[0050] FTIR analysis of the imidized films was carried out on a Varian 670-IR equipped with a Diamond GladiATR attachment. Spectral data were collected at 4 cm -1 The images were acquired at a resolution of .

[0051] Compression molding was performed on a Carver Model No. 3856 using two stainless steel plates covered with KAPTON film coated with PARTALL Power Glossy Liquid (Rexco) release agent to produce clear, ductile films. Film thickness was controlled using 16 mil thick steel shims.

[0052] Melt flow rheology, N 2 Rheological studies were carried out at ambient temperature on a TA Instruments Discovery Hybrid Rheometer (DHR)-2 using a disposable aluminum parallel plate geometry with 8 mm diameter. The linear viscoelastic region (LVR) was explored by strain sweep tests from 0.01-10% oscillatory strain at 1 Hz. Complex viscosity (η* ) as well as storage (G') and loss moduli (G") were obtained. TA Instruments software (TRIOS) created a master curve by shifting the viscosity and modulus. Melt flow characterization involved a power law analysis of the shear thinning regime. A 3600 s time sweep at 1 Hz and 1.25% strain amplitude monitored the viscosity and modulus as a function of time to induce crosslinking in the molten state.

[0053] Flammability tests were performed according to the procedures of Underwriter's Laboratory Bulletin 94 (UL94) entitled "Tests for Flammability of Plastic Materials, UL 94". Several ratings are applicable based on the burning rate, time to extinguishment, ability to resist dripping, and whether the dripping is burning or not. The thickness of the bars was 0.4 mm. Flame retardancy ratings were characterized by the UL-94 vertical burn test according to the ASTM D3801 standard. In each test, a flame was applied to the sample for 10 seconds (s) and then removed. The self-extinguishing time was measured as t 1 The flame was then applied again for another 10 seconds and the self-extinguishing time was recorded as t 2 Recorded as (s).

[0054] Example 1: Synthesis of DABA-PAA and DABA-PEI Diaminobenzoic acid substituted polyamic acid (DABA-PAA) and diaminobenzoic acid substituted polyetherimide (DABA-PEI) were prepared as follows.

[0055] M of 20,000 g / mol nThe synthesis of DABA-PEI with, as an example, follows targeting 50 mol% DABA based on the total moles of diamines used to prepare the polymer. DABA (3.02 g, 19.6 mmol), mPD (2.12 g, 19.6 mmol), BPA-DA (20.00 g, 37.8 mmol), and NMP (92 mL) were placed in a three-neck, 500 mL, round-bottom flask. The flask was then equipped with a glass stirring rod fitted with a stirring blade, a rubber septum, and a Dean-Stark trap topped with a condenser. The contents were purged with nitrogen for 20 min with slow stirring. The reaction mixture was stirred at 75-100 rpm for 18 h at 23 °C until the components were dissolved. PA (0.42 g, 2.9 mmol) was then added as an end-capping reagent. The resulting product solution was then either precipitated into methanol and isolated as DABA-PAA, or the solution was solvent cast to produce a DABA-PAA film, which was then imidized by heating to form a DABA-PEI film.

[0056] Alternatively, a reaction mixture containing DABA, mPD, BPA-DA, and NMP was heated at 180° C. with stirring at 75-100 rpm for 18 hours. PA was then added to the reaction mixture. The products were isolated either by precipitation or by solution casting of films.

[0057] A similar procedure was used to prepare DABA-PAA and DABA-PEI with 10, 25, and 75 mol% DABA incorporation. Additional samples containing 100 mol% DABA were also prepared by omitting mPD from the above synthesis procedure.

[0058] 1 H NMR spectroscopy was used to determine the incorporation of DABA (mol%) and M n was determined by end-group analysis of the chemical shifts associated with the PA aromatic protons.

[0059] As seen in Scheme 1 , poly(amic acid) (PAA) synthesized at room temperature proceeded via a one-pot, two-step reaction to afford linear polymers. (Scheme 1) [ka]

[0060] Example 2: Imidization of DABA-PAA For DABA-PAA, solution casting was used to generate films and analyze the imidization temperature. Samples cast on glass slides / plates were heated at 80° C., 150° C., or 200° C. and then subjected to imidization temperature analysis. After the films were isolated and dried, the temperature required for complete imidization (T im TGA was performed in a stepwise fashion to determine T im was explored, where a change of more than 0.1 wt% / min prompted an isothermal step to continue until a change of less than 0.01 wt% / min occurred, and heating and isothermal steps were repeated until the sample reached 600°C. Using 50 mol% DABA-PAA as an example, films heated to 80°C and 150°C showed an isothermal step at approximately 260°C and a second isothermal step at approximately 480°C to 490°C. DABA-PAA films heated to 200°C showed a slight drop in weight% at approximately 260°C but no isothermal step, while they showed an isothermal step in the 480°C to 490°C range. Without wishing to be bound by theory, it is believed that the first isothermal step occurs due to volatilization of the NMP solvent and thermal imidization. T im was determined as the temperature of the isothermal step plus 10°C. im These temperatures were confirmed by FTIR analysis of films heated to

[0061] Further analysis was performed on samples heated at 150° C. The compositions showed two isothermal steps by TGA after heating at 150° C. The first isothermal step occurred between 250° C. and 300° C. Higher mol% DABA incorporation increased the temperature of the first step. The first isothermal step plus 10° C. was the T of each composition. im It was decided. im increased linearly with increasing mol% incorporation of DABA comonomer up to 300 °C for 100 mol% DABA-PEI. im and 450 °C, where weight loss began again and continued until the second isothermal step near 520 °C. The second isothermal step occurred due to backbone decomposition, consistent with other PEIs. Without wishing to be bound by theory, the weight loss between 450 °C and the second isothermal step was more pronounced at higher mol% incorporation of DABA, suggesting thermal instability prior to backbone decomposition imparted by the inclusion of carboxylic acid pendant groups.

[0062] Example 3: Thermal properties of DABA-PEI mol% T corresponding to DABA incorporation im The determination of the reaction temperature allowed for the synthesis of PEI on a larger industrial scale. The reaction setup remained consistent with the DABA-PAA synthesis in Example 1, but the reaction was heated to 180 °C to directly obtain the DABA-PEI sample. After completion of the synthesis, the reaction flask was placed in a suitable T im The imidization was completed by heating to RT to remove the NMP solvent. The sample was redissolved in NMP and solvent cast to give a clear, ductile film. TGA of the fully imidized DABA-PEI revealed no weight loss until approximately 450 °C, with earlier weight loss onset for PEI with higher mol% DABA incorporation, consistent with the TGA analysis of DABA-PAA.

[0063] Differential scanning calorimetry (DSC) revealed that the T g It was decided to increase T im T g When normalized by T, all compositions undergo complete imidization atg It was found that imidization required a similar temperature (approximately 45° C.) above 100° C. As mentioned above, the imidization temperature increased linearly with increasing DABA incorporation.

[0064] The thermal properties of DABA-PEI are shown in Table 2.

[0065] [Table 2]

[0066] Example 4: DMA analysis of DABA-PEI Dynamic mechanical analysis (DMA) was used to explore the thermomechanical performance over a range of temperatures. DABA-PEI significantly improved the T g The rest of the story became clear, and T g The plateau extending beyond 400° C. indicated crosslinking.

[0067] Example 5: FTIR analysis of DABA-PEI To further understand the decarboxylation and crosslinking for this system, a TGA coupled to FTIR was used to monitor and analyze the off-gas from the TGA furnace. 20 mg films of equal size and shape were heated to probe the chemical composition of the off-gas. The first volatile compound was the NMP solvent, between 10 and 20 minutes. Following this peak, for the 100 mol% DABA-PEI sample, CO 2 / CO, and for 0 mol% DABA-PEI, CO 2 There was no CO peak, indicating a relationship between the peak and the amount of initial DABA monomer incorporated in the sample. 2 Skeletal degradation was observed >80 min after the CO peak. Similar peak wavenumbers and intensities were observed between both samples. 2 Further analysis of the intensity of the Gram-Schmidt plot versus mol% DABA incorporation at the time corresponding to maximum removal of / CO revealed a linear relationship, allowing quantification of decarboxylation during different processing steps.

[0068] Example 6: Branching of DABA-PEI The reactivity of the pendant carboxylic acid groups at elevated temperatures provided reactive branching in the melt. Using a rheometer, melt time sweeps of 0 mol%, 5 mol%, and 10 mol% DABA-PEI at 340 °C were performed to target melt-induced crosslinking. All samples were run at a target M of 20,000 g / mol. n With N up to 300°C 2 Heating under atmosphere ensured complete imidization prior to rheological analysis; therefore, some cross-linking may have occurred during initial imidization. Samples containing DABA had a smaller gap between storage (G') and loss (G") moduli over the entire time sweep compared to the control PEI. The samples maintained a larger G" relative to G' over time, suggesting the absence of cross-linking. DSC showed T for the samples after the time sweep. g A minimal shift in was observed, but the slight broadening of the transition suggests a slight change in the polymer structure.

[0069] Advanced Permeation Chromatography (APC) analyzed the relative molecular weight and polydispersity (PDI) of the PEI control and 5 mol% DABA-PEI. 10 mol% DABA-PEI produced a heterogeneous solution and was unsuitable for APC analysis. The control PEI had similar relative M w The CHCl concentration in the 5 mol% DABA-PEI sample increased linearly with time, whereas the CHCl concentration in the 5 mol% DABA-PEI sample increased linearly with time. 3 The corresponding increase in PDI to >2.0 with solubility in suggests branching for the polymer growing in a stepwise fashion. Therefore, changes in viscoelastic behavior and rheological performance were expected after treatment and were further analyzed by melt rheology for samples treated for 60 min.

[0070] The viscoelastic response was probed by a frequency sweep in 10 °C increments between 340 °C and 220 °C. The complex viscosity (η *) Master curves revealed a Newtonian plateau for the control PEI sample, but no plateaus were discernible for both the 5 mol% and 10 mol% DABA-PEI samples. The 10 mol% DABA-PEI sample exhibited the highest η at the lowest frequency. * The maximum branching amount and potential M w DABA-PEI at 5 mol% showed a slightly lower M w Even if we have a higher η * Without wishing to be bound by theory, a low branching density results in increased entanglements per chain, which is usually * This affects the flow behavior at low shear rates beyond the usual reduction in coil size that reduces the shear rate. As higher frequencies are reached, significant shear thinning begins and progresses over frequencies of 2-3 decades, most of which are commonly used in processes such as injection molding.

[0071] <Example 7: Flame retardancy> Table 3 shows the thermal properties and flame retardancy of the PEI compounds.

[0072] [Table 3]

[0073] As shown in Table 3, the control PEI sample (0.4 mm thick) showed dripping in all samples and ignited the cotton in 6 of 7 tests, consistent with the UL-certified, 94V-2 flame class rating at 0.4 mm thickness for the commercial PEI samples. Samples with 5 mol% and 10 mol% DABA-PEI showed lower t 1 and t 2 It had an after-flame time and no afterglow. None of the samples had drips and the cotton ignited, therefore the samples achieved a UL94V0 rating. Crosslinking in DABA-PEI improved the flame retardancy.

[0074] This disclosure is further illustrated by the following non-limiting embodiments.

[0075] Aspect 1. A first repeat unit derived from the polymerization of an aromatic dianhydride and a first diamine, the first diamine comprising a carboxyl-substituted C 6-24 a first repeat unit comprising an aromatic hydrocarbon group and, optionally, a second repeat unit derived from the polymerization of an aromatic dianhydride and a second diamine, the second diamine being C 1-30 and a second repeat unit comprising a divalent hydrocarbon group (optionally containing 1 to 4 heteroatoms), wherein the self-branched polyetherimide is endcapped with phthalic anhydride.

[0076] Embodiment 2. The self-branched polyetherimide of embodiment 1, wherein the first repeat unit is represented by formula (1) and the second repeat unit is represented by formula (2): [ka] (1) [ka] (2) wherein each Z is independently an aromatic C optionally substituted with 1 to 6 heteroatoms, 1 to 8 halogen atoms, or a combination thereof. 6-24 A monocyclic or polycyclic moiety, provided that the valence of each R does not exceed the valence of Z. 1 are independently a group of formula (3): [ka] (3) In the formula, each L 1 are independently a single bond or a divalent linking group, and preferably the divalent linking group is a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 1-30Heteroarylene, -O-, -C(O)-, -C(O)-O-, -N(R 2b )-, -S-, or -S(O) 2 -, wherein R 2b is hydrogen, linear or branched C 1-20 Alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 1-20 heterocycloalkyl, and each R 3 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted C 1-30 heteroaryl, preferably hydrogen, n is an integer from 1 to 3, or from 1 to 2, and Each R 2 is independently C 1-30 A self-branching polyetherimide which is a divalent hydrocarbon group, optionally containing 1 to 4 heteroatoms.

[0077] Aspect 3. The self-branched polyetherimide of aspect 2, wherein each R 1 are independently a group of formula (3a): [ka] (3a) In the formula, n1 is an integer from 1 to 3, or from 1 to 2, and preferably, each R 1 are independently a group of formula (3b): [ka] (3b), Self-branching polyetherimide.

[0078] Aspect 4. The self-branched polyetherimide of any one of the preceding aspects, wherein each R 2 is C 6-24 Aromatic hydrocarbon radicals or their halogenated derivatives, linear or branched C2-20 Alkylene group or its halogenated derivative, or C 3-8 A cycloalkylene group or a halogenated derivative thereof, preferably, each R 2 are independently a divalent radical of the formula: [ka] In the formula, Q 1 -O-, -S-, -C(O)-, -SO 2 -, -SO-, -P(R k )(O)-, -C y H 2 - or its halogenated derivatives, or -(C 6 H 10 ) z - and R k is C 1 -8 alkyl or C 6-12 aryl, y is an integer from 1 to 5, and z is an integer from 1 to 4; more preferably, each R 2 are independently meta-phenylene, para-phenylene, bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone, or bis(3,3'-phenylene)sulfone.

[0079] Embodiment 5. The self-branched polyetherimide of any one of the preceding embodiments, wherein each Z is independently derived from a dihydroxy compound of formula (4): [ka] (4) In the formula, each R d and R e are independently a halogen atom or a monovalent C 1-6 is an alkyl group, p' and q' are each independently an integer from 0 to 4; c is an integer from 0 to 4; X a is a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)-, or C 1-18 is an organic bridging group, preferably each Z is independently a divalent group of formula (4a): [ka] (4a) In the formula, J is -O-, -S-, -C(O)-, -SO 2 -, -SO-, or -C y H 2y or its halogenated derivatives, A self-branched polyetherimide, wherein y is an integer from 1 to 5.

[0080] Embodiment 6. The self-branched polyetherimide of any one of the preceding embodiments, each comprising 0.01 to 100 mol%, or 1 to 75 mol%, or 10 to 50 mol% of the first repeat units and 0 to 99.99 mol%, or 25 to 99 mol%, or 50 to 90 mol% of the second repeat units, based on 100 mol% total repeat units of the self-crosslinkable polyetherimide.

[0081] Embodiment 7. The self-branched polyetherimide of any one of the preceding embodiments, having a glass transition temperature greater than 200° C., or from 200 to 400° C., or from 220 to 400° C., or from 220 to 360° C., as determined by differential scanning calorimetry, a thermal decomposition temperature greater than 450° C., or from 450 to 550° C., or from 500 to 550° C., as determined by thermogravimetric analysis at 5% weight loss, or a combination thereof.

[0082] Embodiment 8. A branched polyetherimide derived from thermal decarboxylation and crosslinking of the self-branched polyetherimide of any one of the preceding embodiments.

[0083] Embodiment 9. The branched polyetherimide of embodiment 8, wherein the thermal decarboxylation and crosslinking occurs during melt processing of the self-branched polyetherimide.

[0084] Embodiment 10. The branched polyetherimide of embodiment 8 or 9, wherein the branched polyetherimide has a glass transition temperature greater than 160° C., or from 160 to 300° C., or from 180 to 250° C., or from 200 to 250° C., as determined by differential scanning calorimetry, and a flame retardant rating of V0 at 0.8 mm thickness, or a flame retardant rating of V0 at 0.6 mm thickness, or a flame retardant rating of V0 at 0.4 mm thickness, as measured according to ASTM D3801.

[0085] Aspect 11. A dianhydride of formula (5): [ka] (5) or its chemical equivalent, a condensation reaction product of a first diamine, optionally a second diamine, and phthalic anhydride, wherein the first diamine is represented by formula (6): [ka] (6) In the formula, each L 1 are independently a single bond or a divalent linking group, and each R 3 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted C 1-30 heteroaryl, preferably hydrogen, and n is an integer from 1 to 3, or from 1 to 2; preferably the divalent linking group is a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 1-30 Heteroarylene, -O-, -C(O)-, -C(O)-O-, -N(R 2b )-, -S-, or -S(O) 2-, wherein R 2b is hydrogen, linear or branched C 1-20 Alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 1-20 A heterocycloalkyl, self-branched polyamic acid.

[0086] Embodiment 12. The self-branched polyamic acid of embodiment 11, wherein the first diamine is represented by formula (6a): [ka] (6a) In the formula, n1 is an integer from 1 to 3, preferably 1 or 2; 3 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted C 1-30 Heteroaryl, preferably hydrogen, more preferably the first diamine is represented by formula (6b): [ka] (6b) In the formula, R 3 is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted C 1-30 A self-branching polyamic acid which is heteroaryl, preferably hydrogen.

[0087] Embodiment 13. A method for the preparation of a self-branched polyetherimide, comprising heating the self-branched polyamic acid of embodiment 11 to form a self-branched polyetherimide.

[0088] Example 14. The method of example 13, wherein a solution cast sample of the self-branched polyamic acid forms a self-branched polyetherimide at a temperature of from 250 to 300° C., or from 260 to 300° C., or from 265 to 300° C., as determined by thermogravimetric analysis.

[0089] Embodiment 15. An article comprising a branched polyetherimide obtained from the self-branched polyetherimide of any one of embodiments 1 through 7, a branched polyetherimide of any one of embodiments 8 through 10, or a branched polyetherimide obtained from the self-branched polyamic acid of any one of embodiments 11 or 12, preferably the article is a film, a fiber, a foam, or a molded part.

[0090] The compositions, methods, and articles may optionally comprise, consist of, or consist essentially of any suitable components or steps disclosed herein. The compositions, methods, and articles may additionally, or alternatively, be formulated to be devoid of, or substantially free of, any steps, components, materials, material ingredients, adjuvants, or species that are not otherwise required for the accomplishment of the function or purpose of the compositions, methods, and articles.

[0091] The singular forms "a," "an," or "the" include plural referents unless the context clearly dictates otherwise. "Or" means "and / or" unless the context clearly dictates otherwise. The endpoints of all ranges directed to the same component or property are inclusive and independently combinable. The disclosure of narrower ranges or more specific groups in addition to broader ranges does not negate the broader ranges or larger groups. As used herein, "combinations thereof" is open-ended and means that the combination includes one or more of the recited items, optionally with one or more similar items that are not recited.

[0092] Unless otherwise specified, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. "Combination" includes blends, mixtures, alloys, reaction products, and the like. "Hydrocarbyl" and "hydrocarbon" broadly refer to groups containing carbon and hydrogen, and optionally having one to three heteroatoms, such as oxygen, nitrogen, halogen, silicon, sulfur, or combinations thereof; "alkyl" means a linear or branched, saturated monovalent hydrocarbon group; "alkylene" means a linear or branched, saturated, divalent hydrocarbon group; "alkylidene" means a linear or branched, saturated divalent hydrocarbon group, both valencies being on a single common carbon atom; "alkenyl" means a linear or branched, monovalent hydrocarbon group having at least two carbons joined by a carbon-carbon double bond; "cycloalkyl" means a non-aromatic monovalent monocyclic or polycyclic hydrocarbon group having at least three carbon atoms, and "cycloalkenyl" means a non-aromatic cyclic divalent carbon atom having at least three carbon atoms and having at least one degree of unsaturation.

[0036] "aryl" and "arylene" mean monovalent and divalent radicals, respectively, containing at least one aromatic and optionally non-aromatic ring and having only carbon in the ring or rings; "alkylaryl" means an aryl group substituted with an alkyl group; "arylalkyl" means an alkyl group substituted with an aryl group; "heteroaryl" and "heteroarylene" mean monovalent and divalent aromatic radicals, respectively, in which at least one carbon in the ring is replaced with a heteroatom (S, O, P, or N); "acyl" means an alkyl group bonded through a carbonyl carbon bridge (-C(=O)-); "alkoxy" means an alkyl group bonded through an oxygen bridge (-O-); and "aryloxy" means an aryl group as defined above with the indicated number of carbon atoms bonded through an oxygen bridge (-O-).

[0093] Unless otherwise noted, each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect the synthesis, stability, or use of the compound. Combinations of substituents or variables are permitted. As used herein, "substituted" means that at least one hydrogen on the specified atom or group has been replaced with another group, provided that the normal valence of the specified atom is not exceeded. When a substituent is oxo (=O), two hydrogens on that atom are replaced. Exemplary groups that can be present on a "substituted" position include, but are not limited to, the following: cyano, hydroxyl, nitro, alkanoyl (e.g., C 2-6 Alkanoyl groups, e.g. acyl), carboxamide, C 1-6 or C 1-3 Alkyl, cycloalkyl, alkenyl, and alkynyl, C 1-6 or C 1-3 Alkoxy, C 6-10 Aryloxy, C 1-6 Alkylthio, C 1-6 or C 1-3 Alkylsulfinyl, C 1-6 or C 1-3 Alkyl sulfonyl, amino di(C 1-6 or C 1-3 ) Alkyl, C 6-12 Aryl, C 7-19 Arylalkyl, or C 7-19 Arylalkoxy. If a group is substituted, the indicated number of carbon atoms does not include the carbon atoms of the substituent(s), if any.

[0094] All patents, patent applications, and other references cited are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term in this application takes precedence over the conflicting term in the incorporated reference.

[0095] While particular embodiments have been described, presently unanticipated or unforeseen alternatives, modifications, variations, improvements, and substantial equivalents may occur to the applicant or those skilled in the art, and it is therefore intended that the appended claims, as filed and as they may be amended, shall cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. a first repeat unit derived from the polymerization of an aromatic dianhydride and a first diamine, said first diamine comprising a carboxyl-substituted C ６－２４ a first repeating unit including an aromatic hydrocarbon group; Optionally, a second repeat unit derived from the polymerization of an aromatic dianhydride and a second diamine, said second diamine being C １－３０ a second repeat unit comprising a divalent hydrocarbon group (optionally containing 1 to 4 heteroatoms); A self-branching polyetherimide comprising: A self-branching polyetherimide, wherein the self-branching polyetherimide is end-capped with phthalic anhydride.

2. The first repeat unit is represented by formula (1) and the second repeat unit is represented by formula (2): 【Chemistry 1】 （１） 【Chemistry 2】 （２） During the ceremony, Each Z is independently an aromatic C optionally substituted with 1 to 6 heteroatoms, 1 to 8 halogen atoms, or a combination thereof. ６－２４ a monocyclic or polycyclic moiety, provided that the valence does not exceed the valence of Z; Each R １ are independently a group of formula (3): 【Transformation 3】 （３） During the ceremony, Each L １ are independently a single bond or a divalent linking group, Each R ３ are independently hydrogen, substituted or unsubstituted C １－３０ Alkyl, substituted or unsubstituted C ３－３０ Cycloalkyl, substituted or unsubstituted C １－３０ Heterocycloalkyl, substituted or unsubstituted C ６－３０ Aryl, or substituted or unsubstituted C １－３０ is heteroaryl, n is an integer from 1 to 3, and Each R ２ is independently C １－３０ 2. The self-branching polyetherimide of claim 1, wherein the divalent hydrocarbon group optionally contains from 1 to 4 heteroatoms.

3. Each R １ are independently a group of formula (3a): 【Chemistry 4】 (3a) wherein n1 is an integer from 1 to 3, or Each R １ is independently a group of formula (3b): 【Transformation 5】 (3b), The self-branching polyetherimide according to claim 2.

4. Each R ２ is C ６－２４ Aromatic hydrocarbon groups or halogenated derivatives thereof, linear or branched C ２－２０ an alkylene group or a halogenated derivative thereof, or C ３－８ a cycloalkylene group or a halogenated derivative thereof, or Each R ２ are independently a divalent radical of the formula: 【Transformation 6】 During the ceremony, Q １ -O-, -S-, -C(O)-, -SO ２ -, -SO-, -P(R ｋ ) (O)-, -C ｙ H ２ - or a halogenated derivative thereof, or -(C ６ H １０ ) ｚ - and R ｋ is C １ -8 alkyl or C ６－１２ is aryl, y is an integer from 1 to 5, and z is an integer from 1 to 4; or Each R ２ The self-branching polyetherimide of claim 1, wherein is independently meta-phenylene, para-phenylene, bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone, or bis(3,3'-phenylene)sulfone.

5. Each Z is independently derived from a dihydroxy compound of formula (4): 【Transformation 7】 （４） During the ceremony, Each R ｄ and R ｅ are independently a halogen atom or a monovalent C １－６ is an alkyl group, p' and q' are each independently an integer from 0 to 4; c is 0 to 4, and X ａ is a single bond, -O-, -S-, -S(O)-, -S(O) ２ -, -C(O)-, or C １－１８ is an organic bridging group, or Each Z is independently a divalent group of formula (4a): 【Transformation 8】 (4a) During the ceremony, J is -O-, -S-, -C(O)-, -SO ２ -, -SO-, or -C ｙ H ２ｙ or a halogenated derivative thereof, and 2. The self-branching polyetherimide of claim 1, wherein y is an integer from 1 to 5.

6. each based on 100 mol % total repeat units of the self-crosslinkable polyetherimide, 0.01 to 100 mol % of the first repeat unit; 0 to 99.99 mol % of the second repeat unit; 2. The self-branching polyetherimide of claim 1, comprising:

7. a glass transition temperature greater than 200°C as determined by differential scanning calorimetry; a thermal decomposition temperature of greater than 450°C as determined by thermogravimetric analysis at 5% weight loss, or combinations of these 2. The self-branching polyetherimide of claim 1, comprising:

8. A branched polyetherimide derived from thermal decarboxylation and crosslinking of the self-branching polyetherimide of any one of claims 1 to 7.

9. The branched polyetherimide of claim 8, obtained by melt processing of the self-branching polyetherimide, wherein the branched polyetherimide is provided by the thermal decarboxylation and crosslinking.

10. a glass transition temperature greater than 160°C as determined by differential scanning calorimetry, and Flame retardancy rating of V0 at 0.8 mm thickness when measured according to ASTM D3801; 9. The branched polyetherimide of claim 8, having

11. Dianhydrides of formula (5): 【Chemistry 9】 （５） or its chemical equivalent, a first diamine; optionally a second diamine, and phthalic anhydride, A self-branching polyamic acid comprising a condensation reaction product of The first diamine is represented by formula (6): 【Chemistry 10】 （６） During the ceremony, Each L １ are independently a single bond or a divalent linking group, Each R ３ are independently hydrogen, substituted or unsubstituted C １－３０ Alkyl, substituted or unsubstituted C ３－３０ Cycloalkyl, substituted or unsubstituted C １－３０ Heterocycloalkyl, substituted or unsubstituted C ６－３０ Aryl, or substituted or unsubstituted C １－３０ is heteroaryl, and n is an integer from 1 to 3; or The divalent linking group is a substituted or unsubstituted C １－３０ Alkylene, substituted or unsubstituted C ３－３０ Cycloalkylene, substituted or unsubstituted C １－３０ Heterocycloalkylene, substituted or unsubstituted C ６－３０ Arylene, substituted or unsubstituted C １－３０ Heteroarylene, —O—, —C(O)—, —C(O)—O—, —N(R ２ｂ )-, -S-, or -S(O) ２ -, where R ２ｂ is hydrogen, straight or branched C １－２０ Alkyl, monocyclic or polycyclic C ３－２０ Cycloalkyl, or monocyclic or polycyclic C １－２０ Heterocycloalkyl, self-branching polyamic acids.

12. The first diamine is represented by formula (6a): 【Chemistry 11】 (6a) During the ceremony, n1 is an integer from 1 to 3, and Each R ３ are independently hydrogen, substituted or unsubstituted C １－３０ Alkyl, substituted or unsubstituted C ３－３０ Cycloalkyl, substituted or unsubstituted C １－３０ Heterocycloalkyl, substituted or unsubstituted C ６－３０ Aryl, or substituted or unsubstituted C １－３０ is heteroaryl, or The first diamine is represented by formula (6b): 【Chemistry 12】 (6b) During the ceremony, R ３ is hydrogen, substituted or unsubstituted C １－３０ Alkyl, substituted or unsubstituted C ３－３０ Cycloalkyl, substituted or unsubstituted C １－３０ Heterocycloalkyl, substituted or unsubstituted C ６－３０ Aryl, or substituted or unsubstituted C １－３０ The self-branching polyamic acid of claim 11 which is heteroaryl.

13. 12. A method for producing a self-branching polyetherimide, comprising heating the self-branching polyamic acid of claim 11 to form said self-branching polyetherimide.

14. 14. The method of claim 13, wherein a solvent cast sample of the self-branching polyamic acid forms the self-branching polyetherimide at a temperature of 250 to 300° C. as determined by thermogravimetric analysis.

15. An article comprising a branched polyetherimide obtained from the self-branching polyetherimide according to any one of claims 1 to 7, the branched polyetherimide according to claim 8, or the branched polyetherimide obtained from the self-branching polyamic acid according to any one of claims 11 or 12, Optionally, The article is a film, a fiber, a foam, or a molded part.

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